JPH09211801A - Method for processing silver halide photographic sensitive material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a photographic sensitive material processing method less in influence on a human body during handling, excellent in silver tone, high in sensitivity and low in color remaining even in a rapid process, and improved in roller marks. SOLUTION: A silver halide photographic sensitive material having at least one silver halide emulsion layer containing a selenium compd. and/or tellurium compd. and a compd. expressed by the formula R11 -(S)n-R12 is processed with a developer containing a polyhydric alcohol and reductons. In the formula, R11 and R12 are aliphatic groups, aromatic groups, heterocyclic groups or atoms which can form rings by bonding. R11 and R12 may be same or different, and (n) is an integer of 2 to 6.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for processing a silver halide photographic light-sensitive material, and more particularly to a method for processing a silver halide photographic light-sensitive material which has less influence on the human body.

[0002]

2. Description of the Related Art It is strongly desired to solidify a processing agent for silver halide photographic light-sensitive materials from the viewpoint of improving working environment and easiness of handling. Further, from the viewpoint of a safe environment, it is desired to use other developing agents without using hydroquinones which are harmful to the human body.

A technique using reductones as a developing agent that has little effect on the human body is disclosed in Japanese Patent Laid-Open Nos. 7-77781 and 7-7781.
No. 110554 and the like. However, although the effect on the human body is improved, there is a drawback that the silver color tone of the image obtained after processing is deteriorated.

On the other hand, there is a great demand for shortening the processing time of silver halide photographic light-sensitive materials, and medical sensitive materials are particularly highly demanded from the viewpoint of emergency medical care. When the processing time is shortened, it is necessary to improve the sensitivity of the photosensitive material and improve the fog failure due to the pressure received from the roller of the automatic developing machine.

To improve the aspect of Se or Te in recent years
A sensitizing technique using a compound is disclosed in JP-A-3-111838,
No. 3-237450, No. 4-274640, etc. are disclosed. However, there is a drawback that fog tends to rise, and conventional additives for suppressing fog have been insufficient.

Further, in order to improve the above aspect, many techniques of adding latexes to a light-sensitive material have been disclosed such as JP-A-51-130217 and US Pat. No. 3,325,386. However, there is a drawback that the residual color of the sample after processing deteriorates.

[0007]

SUMMARY OF THE INVENTION Therefore, the object of the present invention is to reduce the influence on the human body during handling, to provide an excellent silver tone even when subjected to rapid processing, to reduce the residual color, and to provide a highly sensitive and low fog silver halide. It is an object of the present invention to provide a method for processing a photographic light-sensitive material and a method for processing a silver halide photographic light-sensitive material which has an excellent silver color tone even after rapid processing, has little residual color, and has an improved roller mark.

[0008]

The above object of the present invention is achieved by the following constitution.

1) A silver halide photographic light-sensitive material having at least one silver halide emulsion layer containing a selenium compound and / or tellurium compound and a compound represented by the following general formula (1) is prepared by using a polyhydric alcohol and a reductone. A method of processing a silver halide photographic light-sensitive material, which comprises processing with a developing solution containing a compound.

In the general formula (1) R ₁₁ — (S) n—R ₁₂ , R ₁₁ and R ₁₂ may be an aliphatic group, an aromatic group, a heterocyclic group, or may be bonded to each other to form a ring. Represents a group of atoms. R ₁₁ and R ₁₂ may be the same or different. n
Represents an integer of 2 to 6.

2) A silver halide photographic light-sensitive material having at least one layer containing dextrin and / or dextran is treated with a developer containing a polyhydric alcohol and reductones. Processing method of photographic light-sensitive material.

In the general formula (1) of the present invention, R ₁₁ and R
Examples of the aliphatic group represented by ₁₂ include linear or branched alkyl, alkenyl, alkynyl, or cycloalkyl groups having 1 to 30 carbon atoms, preferably 1 to 20 carbon atoms.
Specifically, methyl, ethyl, propyl, butyl, hexyl, decyl, dodecyl, isopropyl, t-butyl,
2-ethylhexyl, allyl, 2-butenyl, 7-octenyl, propargyl, 2-butynyl, cyclopropyl, cyclopentyl, cyclohexyl, cyclododecyl. Examples of the aromatic group represented by R ₁₁ and R ₁₂ include those having 6 to 20 carbon atoms, and specific examples thereof include phenyl, naphthyl and anthranyl groups. The heterocyclic group represented by R ₁₁ and R ₁₂ may be a monocyclic ring or a condensed ring, and examples thereof include a 5- or 6-membered heterocyclic ring having at least one kind of O, S, and N atoms in the ring. Specifically, pyrrolidine, piperidine, tetrahydrofuran, tetrahydropyran, oxirane, morpholine, thiomorpholine,
Examples include thiopyran, tetrahydrothiophene, pyrrole, pyridine, furan, thiophene, imidazole, pyrazole, oxazole, thiazole, isoxazole, isothiazole, triazole, tetrazole, thiadiazole, oxadiazole, and benzerogues thereof. Examples of the ring formed by R ₁₁ and R ₁₂ include a 4- to 7-membered ring. It is preferably a 5- to 7-membered ring. The preferred group for R ₁₁ and R ₁₂ is a heterocyclic group, more preferably a heteroaromatic group. The aliphatic group, aromatic group, or heterocyclic group represented by R ₁₁ and R ₁₂ may be further substituted, and examples of the substituent include a halogen atom (chlorine atom, bromine atom, etc.), an alkyl group (eg, Methyl group, ethyl group, isopropyl group, hydroxyethyl group, methoxymethyl group, trifluoromethyl group, t-butyl group, etc.), cycloalkyl group (eg, cyclopentyl group, cyclohexyl group, etc.), aralkyl group (eg, benzyl group, 2 -Phenethyl group, etc.), aryl group (for example, phenyl group, naphthyl group, p-tolyl group,
p-chlorophenyl group etc.), alkoxy group (eg methoxy group, ethoxy group, isopropoxy group, n-butoxy group etc.), aryloxy group (eg phenoxy group etc.),
Cyano group, acylamino group (for example, acetylamino group,
Propionylamino group etc.), alkylthio group (eg methylthio group, ethylthio group, n-butylthio group etc.), arylthio group (eg phenylthio group etc.), sulfonylamino group (eg methanesulfonylamino group, benzenesulfonylamino group etc.), ureido Group (for example, 3-methylureido group, 3,3-dimethylureido group, 1,3-
Dimethylureido group etc.), sulfamoylamino group (dimethylsulfamoylamino group etc.), carbamoyl group (eg methylcarbamoyl group, ethylcarbamoyl group, dimethylcarbamoyl group etc.), sulfamoyl group (eg ethylsulfamoyl group, dimethyl Sulfamoyl group etc.), alkoxycarbonyl group (eg methoxycarbonyl group, ethoxycarbonyl group etc.), aryloxycarbonyl group (eg phenoxycarbonyl group etc.), sulfonyl group (eg methanesulfonyl group, butanesulfonyl group, phenylsulfonyl group etc.) ), An acyl group (eg, acetyl group, propanoyl group, butyroyl group, etc.), amino group (methylamino group, ethylamino group, dimethylamino group, etc.), hydroxy group, nitro group, nitroso group, amine oxide group (eg. Pyridine-oxide group), imide group (eg phthalimido group etc.), disulfide group (eg benzene disulfide group, benzothiazolyl 2-disulfide group etc.), heterocyclic group (eg pyridyl group, benzimidazolyl group, benzthiazolyl group, benzoxazolyl group). Group). R ₁₁ and R ₁₂ may have one or more of these substituents. Further, each substituent may be further substituted with the above substituent. n is an integer of 2 or more, preferably 2 to 6, and more preferably n = 2.

Specific examples of the compound represented by the general formula (1) used in the present invention are listed below, but the present invention is not limited thereto.

[0014]

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[0015]

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[0016]

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The selenium sensitizers used in the chemical sensitization of the present invention include a wide variety of selenium compounds. Examples of useful selenium sensitizers include colloidal selenium metal, isoselenocyanates (eg, allyl isoselenocyanate, etc.), selenoureas (eg, N, N-dimethylselenourea, triethyl N, N, N′-selenourea, N, N, N'-trimethyl-N'-heptafluoroselenourea, N, N,
N'-trimethyl-N'-heptafluoropropylcarbonylselenourea, N, N, N'-trimethyl-N'-
4-nitrophenylcarbonyl selenourea etc.), selenoketones (eg selenoacetone, selenoacetophenone etc.), selenoamides (eg selenoacetamide,
N, N-dimethylselenobenzamide, etc.), selenocarboxylic acids and selenoesters (eg, 2-selenopropionic acid, methyl-3-selenobutyrate, etc.), selenophosphates (eg, tri-p-triselenophosphate, etc.) ), Selenides (triphenylphosphine selenide, diethyl selenide, diethyl diselenide, etc.). Particularly preferred selenium sensitizers are selenides, selenoureas, selenamides, and selenium ketones.

The amount of the selenium sensitizer used varies depending on the selenium compound used, silver halide grains, chemical ripening conditions and the like, but generally about 10 ^-8 to 10 ^-4 mol per mol of silver halide is used.

The temperature of chemical ripening using a selenium sensitizer is 4
The range is preferably from 0 to 90 ° C, more preferably from 45 ° C to 80 ° C. Further, the pH is preferably in the range of 4 to 9, and the pAg is preferably in the range of 6.0 to 9.5.

Specific examples of the selenium sensitizer used in the chemical sensitization of the present invention are listed below, but the present invention is not limited to these.

[0021]

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[0022]

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[0023]

[Chemical 6]

In the chemical sensitization of the present invention, examples useful as tellurium sensitizers include telluroureas (eg, N, N).
-Dimethyltellurourea, tetramethyltellurourea, N-
Carboxyethyl-N, N'-dimethyltellurourea,
N, N'-dimethyl-N'phenyltellurourea), phosphine tellurides (eg, tributylphosphine telluride, tricyclohexylphosphine telluride, triisopropylphosphine telluride, butyl-diisopropylphosphine telluride, dibutylphenylphosphine telluride) , Telluroamides (eg, telluroacetamide,
N, N-dimethyltellurobenzamide), telluroketones, telluroesters, isotellocyanates, and the like.

The technique for using the tellurium sensitizer is similar to that for the selenium sensitizer.

In the present invention, it is also preferable to use reduction sensitization together. The reduction sensitization is preferably performed during the growth of silver halide grains. As a method of applying during the growth, not only a method of performing reduction sensitization in a state where silver halide grains are growing, but also a method of performing reduction sensitization in a state where growth of silver halide grains is interrupted, and then performing reduction sensitization. It also includes a method of growing the perceived silver halide grains.

In the present invention, sensitization with a noble metal salt such as a sulfur compound or a gold salt is also possible. Further, reduction sensitization can be performed, and sensitization can be performed by combining these methods.

Specific examples of the sulfur sensitizer applicable to the present invention include thiourea derivatives such as 1,3-diphenylthiourea, triethylthiourea, 1-ethyl, 3- (2-thiazolyl) thiourea, and rhodanine derivatives. Preferred examples include dithiacarbamic acids, polysulfide organic compounds, and simple sulfur. In addition, as the simple substance of sulfur, α-sulfur belonging to the orthorhombic system is preferable.

As a gold sensitizer, chloroauric acid, gold thiosulfate,
In addition to gold thiocyanate, thioureas, rhodanines,
Other examples include gold complexes of various compounds.

The amount of sulfur sensitizer and gold sensitizer used is not uniform depending on the type of silver halide emulsion, the type of compound used, ripening conditions, etc.
It is preferably from 1 × 10 ^-4 mol to 1 × 10 ^-9 mol per mol. More preferably, 1 × 10 ⁻⁵ mol to 1 × 1
^0-8 mol.

The sulfur sensitizer and the gold sensitizer may be added by dissolving them in water or alcohols, other inorganic or organic solvents and adding them in the form of a solution. It may be added in the form of a dispersion obtained by emulsifying and dispersing using such a medium. Both sulfur sensitization and gold sensitization may be performed simultaneously, or may be performed separately and stepwise. In the latter case, favorable results may be obtained if gold sensitization is performed after or during sulfur sensitization appropriately.

Reduction sensitization is carried out by adding a reducing agent and / or a water-soluble silver salt to the silver halide emulsion, as is carried out during the growth of silver halide grains of the silver halide emulsion. Preferred examples of the reducing agent include thiourea dioxide and ascorbic acid and derivatives thereof.
Other preferable reducing agents include hydrazine, polyamines such as diethylenetriamine, dimethylamineboranes, sulfites and the like.

The silver halide composition of the silver halide emulsion used in the present invention may have any composition, for example, silver chloride, silver iodochloride, silver chlorobromide, silver bromide, silver iodobromide, silver chloroiodobromide and the like. Any of the above silver halides may be used. The silver iodide content in the case of containing silver iodochloride is preferably 0 mol% or more and 1.5 mol% or less, and 0 mol% or more and 1.0 mol% or less, as an average silver iodide content in the entire silver halide grains. Is more preferable.

The average grain size of the silver halide grains used in the present invention is preferably 0.15 to 5.0 μm,
The thickness is more preferably 0.2 to 3.0 μm, and most preferably 0.2 to 2.0 μm.

The crystal habit of the silver halide grains may be any of those having a cubic, octahedral or twin plane, but tabular silver halide grains are preferred.

The tabular silver halide grain means a grain having two parallel main planes facing each other, and one which can be used in the present invention may be one having a (111) plane as the main plane.
The (00) plane may be either a main plane or either plane. The tabular silver halide grains that can be used in the present invention have a ratio of grain size to grain thickness (hereinafter referred to as aspect ratio) of 2 or more, but preferably 2.0 or more and less than 15.0.
It is particularly preferably 3 or more and less than 10.

Here, the grain size means an average projected area diameter (hereinafter referred to as a grain size), which is a circle equivalent diameter of the projected area of the tabular silver halide grains (the same projected area as the silver halide grains is The diameter of a circle having a thickness), and the thickness means a distance between two parallel principal planes forming a tabular silver halide grain.

When tabular silver halide grains are used in the present invention, the average thickness is preferably 0.01 to 1.0 μm, more preferably 0.02 to 0.60 μm, and further preferably 0.05. Is about 0.50 μm. The average particle diameter is preferably 0.15 to 5.0 μm, and 0.4 to
More preferably, it is 3.0 μm, most preferably 0.4 to 2.0 μm. The tabular silver halide grains are preferably monodisperse emulsions having a narrow grain size distribution. Specifically, (standard deviation of grain size / average grain size) × 100 = width of grain size distribution (%) Is preferably 25% or less, more preferably 20% or less, and particularly preferably 15% or less.

When tabular silver halide grains are used in the present invention, they can be prepared by the method described in US Pat. No. 5,320,938. That is, it is preferable to nucleate with low pCl in the presence of iodide ions under the condition that the (100) plane is easily formed. After nucleation, Ostwald ripening and / or growth can be performed to obtain tabular silver halide grains having a desired grain size and distribution.

The tabular silver halide grains may be formed of a cadmium salt during the grain forming process and / or the growing process.
Metal ions are added using at least one selected from zinc salt, lead salt, thallium salt, iridium salt (including complex salt), rhodium salt (including complex salt), and iron salt (including complex salt), and the inside of the particle is added. And / or these metal elements may be contained on the particle surface.

The tabular silver halide grains used in the present invention must be spectrally sensitized with methine dyes and the like. The sensitizing dyes used in the light-sensitive material of the present invention include cyanine dyes, merocyanine dyes, complex cyanine dyes, complex merocyanine dyes, holoboler cyanine dyes, hemicyanine dyes, styryl dyes and hemioxonol dyes. Particularly useful dyes are those belonging to the cyanine dyes, merocyanine dyes and complex merocyanine dyes.

These dyes can be applied to any of the commonly used nuclei. That is, a pyrroline nucleus, an oxazoline nucleus, a thiazoline nucleus, a pyrrole nucleus, an oxazole nucleus, a thiazole nucleus, a selenazole nucleus, an imidazole nucleus, a tetrazole nucleus, a pyridine nucleus, etc. A renin nucleus, a benzindolenin nucleus, an indole nucleus, a naphthoxazole nucleus, a benzothiazole nucleus, a naphthothiazole nucleus, a benzoselenazole nucleus, a benzimidazole nucleus, a quinoline nucleus, and the like can be applied. These nuclei may have a substituent on a carbon atom.

In the merocyanine dye or the complex merocyanine dye, pyrazoline-containing nuclei having a ketomethine structure are used.
5-6 nuclei, thiohydantoin nuclei, 2-thiooxazolidine-2,4-dione nuclei, thiazoline-2,4-dione nuclei, rhodanine nuclei, thiobarbituric acid nuclei, etc.
Member heterocyclic nuclei can be applied.

These sensitizing dyes may be used alone or in combination, and the combination is often used particularly for the purpose of supersensitization. In addition, the emulsion layer may contain, in addition to the sensitizing dye, a dye having no spectral sensitization or a substance which does not substantially absorb visible light and exhibits a supersensitizing effect. For example, it may contain a substituted aminostilbene compound having a nitrogen-containing heterocyclic nucleus group, an aromatic organic acid formaldehyde condensate, a cadmium salt, an azaindene compound and the like.

The spectral sensitizing dye is preferably added as a solid fine particle dispersion rather than as a solution of an organic solvent. In particular, it is preferable to disperse it in an aqueous system in which substantially no organic solvent and / or surfactant is present, and to add it in the form of a solid fine particle dispersion that is substantially insoluble in water. The particle size after dispersion is preferably 1 μm or less.

In the processing method of the silver halide photographic light-sensitive material of the present invention, the processing is carried out with an alkaline developer containing reductones. The reductones referred to in the present invention are compounds represented by the following general formula [A].

[0047]

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In the formula, R ₁ and R ₂ each independently represent a substituted or unsubstituted alkyl group, a substituted or unsubstituted amino group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted alkylthio group, R ₁ and R ₂ may combine with each other to form a ring. k represents 0 or 1, and when k is 1, X is -CO-
Or represents -CS-.

In the compound represented by the general formula [A], a compound represented by the following general formula [A-a] in which R ₁ and R ₂ are bonded to each other to form a ring is preferable.

[0050]

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In the formula, R ₃ is a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted amino group, a substituted or unsubstituted alkoxy group, a sulfo group, a carboxyl group, Amide group, sulfonamide group, Y ₁ represents O or S, Y ₂ represents O, S or NR
Represents ₄ . R ₄ represents a substituted or unsubstituted alkyl group or a substituted or unsubstituted aryl group.

The alkyl group in formula [A] or formula [A-a] is preferably a lower alkyl group, for example, an alkyl group having 1 to 5 carbon atoms, and the amino group is an unsubstituted amino group. Alternatively, an amino group substituted with a lower alkyl group is preferable, a lower alkoxy group is preferable as the alkoxy group, a phenyl group or a naphthyl group is preferable as the aryl group, and these groups may have a substituent. Often, the substitutable group is preferably a hydroxyl group, a halogen atom, an alkoxy group, a sulfo group, a carboxyl group, an amide group or a sulfonamide group. Substituents and the above general formula [A] according to the present invention
Alternatively, specific compound examples represented by the general formula [Aa] are shown below, but the present invention is not limited thereto.

[0053]

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[0054]

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These compounds are typically ascorbic acid or erythorbic acid or derivatives derived from them, and they are available as commercial products or can be easily synthesized by known synthetic methods.

Dextrin or dextran is used in the silver halide photographic light-sensitive material of the present invention. Dextrin and dextran may be used alone or in combination.

The molecular weight is not particularly limited, but preferably 1
It is preferably 000 or more and 700,000 or less, and particularly preferably 1000 or more and 100,000 or less.

The lower limit of the amount added is preferably 0.01 g / m ² , more preferably 0.05 g / m ² , especially 0.1 g.
/ M ² is preferred. The upper limit of the amount added is preferably ² g / m ² , more preferably 1 g / m ² , and particularly preferably 0.5 g / m ² .

The polyhydric alcohol of the present invention has 2 to 1 hydroxyl groups.
It has 2 carbon atoms and 2 to 20 carbon atoms and is solid at room temperature. The polyhydric alcohol of the present invention may be used alone or in combination of two or more.

Specific preferred examples of the above polyhydric alcohols will be given below, but the present invention is not limited thereto.

2-1. D-trait 2-2. L-trait 2-3. meso-trait 2-4. Adnit 2-5. D-arabit 2-6. L-arabit 2-7. Adnit 2-8. Xylit 2-9. D-Sorbit 2-10. L-Sorbit 2-11. D-Mannit 2-12. D-idit 2-13. D-talit 2-14. Zulsit 2-15. Alit 2-16. Perseit 2-17. Borremit 2-18. β-sedoheptit 2-19. meso-inosit.

The treatment method of the present invention is preferably a method using a solid treatment agent. To solidify the photographic processing agent, concentrate or fine powder or granular photographic processing agent and water-soluble binder are kneaded and molded, or the surface of the tentatively molded photographic processing agent is sprayed with water-soluble binder. By doing so, any means such as forming a coating layer can be adopted (Japanese Patent Application Laid-Open No. 4-29136, 4).
-85535, 4-85536, 4-8553
No. 3, No. 4-85534, No. 4-172341).

A preferable tablet manufacturing method is a method in which a solid processing agent in powder form is granulated and then a tableting step is performed to form the tablet. There is an advantage that the solubility and the storability are improved and the photographic performance becomes stable as compared with the solid processing agent formed by the tableting step by simply mixing the solid processing agent components.

As a granulation method for tablet formation, known methods such as tumbling granulation, extrusion granulation, compression granulation, pulverization granulation, stirring granulation, fluidized bed granulation, and spray drying granulation are used. Can be done.
For tablet formation, the average particle size of the obtained granulated product is 100 to 800 μm in that, when the granulated product is mixed and compressed under pressure, the components become non-uniform, so-called segregation is unlikely to occur.
It is preferred to use
７750 μm. Furthermore, the particle size distribution is
Preferably, 0% or more is within a deviation of ± 100 to 150 μm. Next, when the obtained granules are compressed under pressure, a known compressor, for example, a hydraulic press, a single-shot tableting machine, a rotary tableting machine, or a pre-ketting machine can be used. The solid processing agent obtained by pressurizing and compression can take any shape, but from the viewpoint of productivity, handleability, or the problem of dust when used on the user side, a cylindrical, so-called tablet is used. preferable.

More preferably, at the time of granulation, the above-mentioned effects become more remarkable by separately granulating each component, for example, an alkali agent, a reducing agent, a preservative and the like.

A method for producing a tablet processing agent is described in, for example, JP-A Nos. 51-61837, 54-155038 and 52.
No. 88025, British Patent No. 1213808, etc., and can be produced by a general method. Further, granulating agents are described in, for example, JP-A Nos. 2-10942 and 2-109.
It can be produced by a general method described in the specification of JP-A Nos. 043, 3-39735 and 3-39939. Further, the powder treating agent is described in, for example, JP-A-54-13333.
No. 2, British Patent Nos. 725,892 and 729,862, and German Patent No. 3,733,861.

[0067] The bulk density of the solid processing agent, and in view of its solubility, if a tablet from the viewpoint of the effect of the object of the present invention 1.0g / cm ³ ~2.5g / cm ³ is preferably 1. 0 g
/ Cm ³ in terms of strength of the obtained solid matter,
If it is less than 2.5 g / cm ³ , it is more preferable in terms of solubility of the obtained solid. When the solid processing agent is a granule or powder, the bulk density is preferably from 0.40 to 0.95 g / cm ³ .

When the solid processing agent is used in the present invention, the solid processing agent is used as a photographic processing agent such as a developing agent, a fixing agent and a rinsing agent, and the effect of the present invention is great in the developing agent.

When the treatment method of the present invention is carried out using a solid treating agent, the surface of the solid treating agent is treated with the general formula [1], [2], [3], [4] described in Japanese Patent Application No. 6-70860. It is desirable to coat with a compound such as. In particular, these are preferably used in combination with a water-soluble polymer or sugar.

Further, it is desirable to use the saccharide compound described in Japanese Patent Application No. 5-186254 and the coating compound described in Japanese Patent Application No. 6-91987.

In the developer used in the present invention, an organic reducing agent can be used as a preservative in addition to sulfite as a preservative. In addition, a chelating agent or a bisulfite adduct of a hardening agent can be used. It is also preferable to add a silver sludge inhibitor. Addition of a cyclodextrin compound is also preferable, and compounds described in JP-A-1-124852 are particularly preferable.

An amine compound may be added to the developer of the present invention, and the compounds described in US Pat. No. 4,269,929 are particularly preferable.

The developer used in the present invention requires the use of a buffering agent, and examples of the buffering agent include sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, trisodium phosphate, tripotassium phosphate. , Dipotassium phosphate, sodium borate, potassium borate, sodium tetraborate (borate), potassium tetraborate, sodium o-hydroxybenzoate (sodium salicylate),
Examples thereof include potassium o-hydroxybenzoate, sodium 5-sulfo-2-hydroxybenzoate (sodium 5-sulfosalicylate), and potassium 5-sulfo-2-hydroxybenzoate (potassium 5-sulfosalicylate).

Examples of development accelerators include thioether compounds, p-phenylenediamine compounds, quaternary ammonium salts, p-aminophenols, amine compounds, polyalkylene oxides, 1-phenyl-3-pyrazolidones, and hydrazine. If desired, compounds, mesoionic compounds, ionic compounds, imidazoles, etc. can be added.

As the antifoggant, an alkali metal halide such as potassium iodide and an organic antifoggant can be used. Examples of the organic antifoggant include benzotriazole, 6-nitrobenzimidazole, 5-nitroisoindazole, 5-methylbenzotriazole, 5-nitrobenzotriazole, 5-chloro-benzotriazole, 2-thiazolyl-benzimidazole, A nitrogen-containing heterocyclic compound such as 2-thiazolylmethyl-benzimidazole, indazole, hydroxyazaindolizine, and adenine can be given as a representative example 1-phenyl-5-mercaptotetrazole.

Further, in the developer composition used in the present invention, if necessary, methyl cellosolve, methanol,
Acetone, dimethylformamide, a cyclodextrin compound and the like can be used as an organic solvent for increasing the solubility of the developing agent.

Furthermore, other various additives such as stain inhibitors, sludge inhibitors, and stacking effect accelerators can be used.

A compound known as a fixing agent can be added to the fixing agent used in the present invention. Fixing agent, chelating agent, p
An H buffer, a hardener, a preservative, and the like can be added. These are described in, for example, JP-A-4-242246 (p. 4) and JP-A-5-15-1.
The thing described in No. 13632 (pages 2-4) can be used. In addition, Japanese Patent Application No. 4-586323 (20)
(Page 21), a bisulfite adduct of the hardener described in (page 21) and a known fixing accelerator can also be used.

Prior to the treatment, it is also preferable to add a starter, and it is also preferable to solidify and add the starter. As the starter, in addition to an organic acid such as a polycarboxylic acid compound, a halide of an alkaline earth metal such as KBr, an organic inhibitor, and a development accelerator are used.

The emulsion used in the silver halide photographic light-sensitive material of the present invention can use various photographic additives in the steps before and after physical ripening or chemical ripening.

Examples of the compound used in such a process include Research Disclosure (RD) N
o. 17643 (December 1978), (RD) No.
18716 (November 1979) and (RD) No. 3
Various compounds described in 08119 (December 1989) can be used. These three (RD)
The types and locations of the compounds described in are listed below.

Additive RD-17643 RD-18716 RD-308119 Page Classification Page Page Classification Chemical sensitizer 23 III 648 Upper right 996 III Sensitizing dye 23 IV 648-649 996-8 IVA Desensitizing dye 23 IV 998 IVB Dye 25-26 VIII 649-650 1003 VIII Development accelerator 29 XXI 648 Upper right fog inhibitor / stabilizer 24 IV 649 Upper right 1006-7 VI Whitening agent 24 V 998 V Hardener 26 X 651 Left 1004-5 X Surfactant Agent 26-27 XI 650 Right 1005-6 XI Antistatic Agent 27 XII 650 Right 1006-7 XIII Plasticizer 27 XII 650 Right 1006 XII Sliding Agent 27 XII Matting Agent 28 XVI 650 Right 1008-9 XVI Binder 26 XXII 1003-4 IX Support 28 XVII 1009 XVII Support used in the silver halide photographic light-sensitive material of the present invention Examples of the suitable support include polyethylene terephthalate film, and the support surface is provided with an undercoat layer or corona discharge to improve the adhesiveness of the coating layer. Or UV irradiation may be applied.

The hydrophilic colloid layer of the silver halide photographic light-sensitive material according to the present invention specifically means a photosensitive or substantially non-photosensitive silver halide emulsion layer, a protective layer, an intermediate layer, a filter layer, It refers to all the constituent layers of a silver halide photographic light-sensitive material such as an ultraviolet absorbing layer, an antihalation layer and a backing layer.

[0084]

EXAMPLES The present invention will be described below in detail with reference to examples, but the present invention is not limited thereto.

Example 1 (Preparation of seed emulsion EM-1) <Solution A> Ocein gelatin 37.5 g KI 0.625 g NaCl 16.5 g Distilled water to 7500 ml <Solution B> Silver nitrate 1500 g Distilled water to 2500 ml <Solution C> KI 4 g NaCl 140 g Distilled water makes 684 ml <Solution D> NaCl 375 g Distilled water makes 1816 ml At 40 ° C., in solution A in the mixing stirrer described in JP-B-58-58288, solution B is added. 684 ml and the total amount of solution C were added over 1 minute. The EAg was adjusted to 149 mV, and after Ostwald ripening for 20 minutes, the entire remaining amount of solution A and the total amount of solution D were added over 40 minutes. Meanwhile, E
Ag was controlled at 149 mV.

Immediately after the completion of the addition, desalting and washing were carried out to obtain a tabular seed emulsion EM-1. The resulting seed emulsion was composed of tabular grains having at least 60% of the total projected area of the silver halide grains having the (100) plane as a main plane, an average thickness of 0.07 μm,
Electron microscope observation revealed that the average diameter was 0.5 μm and the coefficient of variation was 25%.

(Preparation of high silver chloride emulsion EM-2) The following 4
Tabular high silver chloride emulsions were made using different solutions.

[0088] <solution A> ossein gelatin _{29.4g HO- (CH 2 CH 2 O} ) n - (CH [CH 3] CH 2 O) 17 - (CH 2 CH 2 O) m H (n + m = 5~ 7) to 2240Ml with 10% methanol aqueous solution 1.25ml seed emulsion EM-1 0.98 mole equivalent of distilled water and 3000 ml <solution B> 3.50N AgNO ₃ aqueous 2240Ml <solution C> NaCl 455 g of distilled water <solution D> 1.75N NaCl aqueous solution At the following silver potential control amount of 40 ° C., a mixing stirrer described in JP-B-58-58288 was used to simultaneously mix all the amounts of solution B and solution C with solution A (double jet method). Thus, the addition growth was performed for 110 minutes so that the flow rate at the end of addition was three times the flow rate at the start of addition.

During this period, the silver potential was +120 using Solution D.
It controlled so that it might be set to mV. After completion of the addition, precipitation and desalting were performed by the method described below to remove excess salts.

1. The temperature of the reaction mixture after completion of mixing is raised to 40 ° C.
Modified with phenylcarbamoyl group (substitution rate 90%)
Add 20g / AgX1mol of modified gelatin, 56wt%
Acetic acid is added to reduce the pH to 4.30, and the mixture is left standing and decanted.

2.40 ° C. pure water 1.8 liter / AgX
After adding 1 mol and stirring for 10 minutes, the mixture is left standing and decanted.

3. The above step 2 is repeated once.

4. Then, post-gelatin 15g / AgX1
Mol, sodium carbonate, and water are added to adjust the pH to 6.0, and the mixture is dispersed to 450 ml / AgX1 mol.

Approximately 3,000 emulsions EM-2 thus obtained were observed and measured by an electron microscope to analyze the shape, and 80% or more of the total projected area had the (100) plane as the main plane.
The tabular grains had an average diameter of 1.17 μm and an average thickness of 0.12 μm, and the coefficient of variation was 24%.

(Chemical Sensitization of Emulsion) Subsequently, the high silver chloride emulsion EM-2 was heated to 55 ° C., and then the compound represented by the general formula (1) shown in Table 1 was added at 2 × 10 5 per mol of silver halide.
After the addition of ^-6 mol, the following predetermined amounts of silver iodide fine particles and spectral sensitizing dye were added as a solid fine particle dispersion. Thereafter, a sulfur sensitizer, a selenium sensitizer, and a gold sensitizer are further added, and ripening is performed for a total of 90 minutes. At the end of ripening, 4-hydroxy-6-methyl-1,3,3a, 7- is used as a stabilizer. Tetrazaindene (TAI) was added.

Silver iodide fine grain emulsion (*) equivalent to 5 mmol Spectral sensitizing dye (1) 300 mg Spectral sensitizing dye (2) 30 mg Sulfur sensitizer 2.0 mg Gold sensitizer 1.0 mg Selenium sensitizer (triphenyl Phosphine selenide) 1.0 mg Stabilizer (TAI) 50 mg (*) 5.0 wt% containing 0.06 mol of potassium iodide
2 liters each of an aqueous solution containing 7.06 moles of silver nitrate and 7.06 moles of potassium iodide was added to 6.64 liters of the gelatin aqueous solution of 10 minutes over 10 minutes. During the fine particle formation, the pH was controlled at 2.0 using nitric acid, and the temperature was controlled at 40 ° C. After forming the particles, the pH was adjusted to 6.0 using an aqueous sodium carbonate solution.

[0097]

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The spectral sensitizing dye was prepared as a solid fine particle dispersion according to the method described in JP-A-5-297496. That is, a predetermined amount of the spectral sensitizing dye is added to water whose temperature has been previously adjusted to 27 ° C., and a high-speed stirrer (dissolver) is used at 3.500 rpm
m by stirring for 30-120 minutes.

The above dispersion liquid of the selenium sensitizer was prepared as follows. That is, 120 g of triphenylphosphine selenide was added to 30 kg of ethyl acetate at 50 ° C., stirred and completely dissolved. 3.8 kg of photographic gelatin on the other hand
Was dissolved in 38 kg of pure water, and 93 g of a 25 wt% aqueous solution of sodium dodecylbenzenesulfonate was added thereto. Next, these two liquids were mixed and dispersed by a high-speed stirring type disperser having a dissolver having a diameter of 10 cm at 50 ° C. at a peripheral speed of the dispersion blade of 40 m / sec for 30 minutes. Immediately after that, the residual concentration of ethyl acetate was reduced to 0.3 under reduced pressure.
Ethyl acetate was removed while stirring until the amount became less than wt%. Then, this dispersion is diluted with pure water to 80 kg.
Finished. A part of the dispersion thus obtained was fractionated and used in the above experiment.

(Preparation of coating liquid and coating)
A polyethylene terephthalate film base for X-rays colored in blue (thickness: 175 μm) was previously coated with the following transverse light shielding layers on both sides of the support. Was simultaneously multilayer coated so as to have the following predetermined coating amounts, and dried to obtain coating samples 1 to 4.

The additives used in the coating liquid are as follows. The addition amount is shown as an amount per 1 m ^{2 of} silver halide.

First layer (transverse light shielding layer) Solid fine particle dispersion dye (AH) 180 mg / m ² Gelatin 0.2 g / m ² Sodium dodecylbenzenesulfonate 5 mg / m ² Compound (I) 5 mg / m ² 2, 4-dichloro-6-hydroxy-1,3,5-triazine sodium salt 5 mg / m ² colloidal silica (average particle size 0.014 μm) 10 mg / m ² second layer (emulsion layer) In each emulsion obtained above. The following various additives were added.

Compound (G) 0.5 mg /
m ² 2,6-bis (hydroxyamino) -4-diethylamino-1,3,5-triazine 5 mg / m ² t-butyl-catechol 130 mg / m ² polyvinylpyrrolidone (molecular weight 10,000) 35 mg / m ² styrene- Maleic anhydride copolymer 80 mg / m ² Sodium polystyrene sulfonate 80 mg / m ² Trimethylolpropane 350 mg / m ² Diethylene glycol 50 mg / m ² Nitrophenyl-triphenyl-phosphonium chloride 20 mg / m ² 1,3-Dihydroxybenzene-4 -Ammonium sulfonate 500 mg / m ² 2-Mercaptobenzimidazole-5-sodium sulfonate 5 mg / m ² Compound (H) 0.5 mg / m ² n-C ₄ H ₉ OCH ₂ CH (OH) CH ₂ N (CH ₂ COOH) ₂ 350 mg / m ² compound Material (M) 5 mg / m ² compound (N) 5 mg / m ² compound (P) 0.2 g / m ² compound (Q) 0.2 g / m ² However, as gelatin, 0.8 g / m ² Adjusted to.

Third Layer (Protective Layer) Gelatin 0.6 g / m ² Polymethylmethacrylate matting agent (area average particle size 7.0 μm) 50 mg / m ² formaldehyde 20 mg / m ² 2,4-dichloro-6- Hydroxy-1,3,5-triazine sodium salt 10 mg / m ² bis-vinylsulfonylmethyl ether 36 mg / m ² polyacrylamide (average molecular weight 10000) 0.1 g / m ² sodium polyacrylate 30 mg / m ² polysiloxane ( S1) 20 mg / m ² compound (I) 12 mg / m ² compound (J) 2 mg / m ² compound (S-1) 7 mg / m ² compound (K) 15 mg / m ² compound (O) 50 mg / m ² compound ( ^{S-2) 5mg / m 2} C 9 F 19 -O- (CH 2 CH 2 O) 11 -H 3mg / m 2 C 8 F 17 SO 2 N- (C 3 H 7 _{(CH 2 CH 2 O) 15} -H 2mg / m 2 C 8 F 17 SO 2 N- (C 3 H 7) (CH 2 CH 2 O) 4 - (CH 2) 4 SO 3 Na 1mg / m 2 Hardness Membrane agent (B) 60 mg / m ²

[0105]

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[0106]

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[0107]

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The coating amount of the above materials was for one side, and the coating amount of the emulsion layer was adjusted so as to be 1.3 g / m ² for one side.

(Evaluation of Sensitivity) The obtained sample was sandwiched between two fluorescent intensifying screens (KO-250), irradiated with X-ray through Penetrometer B type (manufactured by Konica Medical Co., Ltd.), and then SRX.
-502 An automatic developing machine was used to modify the processing time so that the processing time was as follows, and processing was performed with the following processing agents at a developing temperature of 35 ° C (all manufactured by Konica Corporation).

At this time, the replenishment amount of the processing solution was 90 ml / m ^{2 for} both the developing solution and the fixing solution. Sensitivity is developed sample N
o. 1 is a relative value with the reciprocal of the amount of X-ray exposure required to obtain a density of minimum density +1.0 being 100.

(Preparation of Development Processing Agent) The following operations (A to
According to D), a developing replenishing tablet and a fixing replenishing tablet were prepared.

Operation (A) As a developing agent, 13,000 g of sodium erythorbate represented by the general formula [A] is ground in a commercially available bandam mill until the average particle size becomes 10 μm. To this fine powder, 4877 g of sodium sulfite, 975 g of phenidone, DTPA1
After adding 635 g and mixing in a mill for 30 minutes and granulating by adding 30 ml of water in a commercially available stirred granulator at room temperature for about 10 minutes, the granulated product was mixed with a fluidized bed drier at 40
After drying at 2 ° C. for 2 hours, the water content of the granules is almost completely removed. The polyhydric alcohol or polyethylene glycol # 6 shown in Table 1 or Table 2 was thus prepared.
After 2167 g of 000 was evenly mixed for 10 minutes using a mixer in a room whose humidity was adjusted to 25 ° C. and 40% RH or less,
The obtained mixture was compressed into tablets with a tableting machine modified from Tough Pressed Collect 1527HU manufactured by Kikusui Seisakusho Co., Ltd. so that the filling amount per tablet was 8.715 g and the mixture was compressed into 2500 tablets.
Tablet A agent for development replenishment was prepared.

Operation (B) 19.500 g of potassium carbonate, 8.15 g of 1-phenyl-5-mercaptotetrazole, sodium hydrogen carbonate 3.
25 g, glutaraldehyde sulfite adduct 650 g, and polyethylene glycol # 6000 (1354 g) are pulverized and granulated in the same manner as in the operation (A). The amount of water added is 30.0
ml, and after granulation, dried at 50 ° C. for 30 minutes to remove almost completely the moisture of the granulated material. The mixture thus obtained was compressed and tableted using the same tableting machine as above at a filling amount per tablet of 9.90 g to prepare 2500 tablets B for replenishment for development.

Procedure (C) 18560 g of ammonium thiosulfate, 1392 g of sodium sulfite, 580 g of sodium hydroxide and 2.32 g of ethylenediaminetetraacetic acid disodium salt are pulverized and granulated in the same manner as in the procedure (A). The amount of water to be added is 500 ml, and after granulation, the granulated material is dried at 60 ° C. for 30 minutes to almost completely remove water from the granulated material. In this way, the mixture thus obtained was packed in a tableting machine as described above at a loading amount of 8.214 per tablet.
g and compression tableting to prepare 2500 fixing supplementary tablets C.

Operation (D) 1860 g of boric acid, 650 aluminum sulfate hydrate 650
0 g, glacial acetic acid 1860 g, sulfuric acid (50% by weight) 925 g
Is pulverized and granulated in the same manner as in the operation (A). The amount of water added is 1
The volume of the granules is adjusted to 00 ml, and after granulation, the granules are dried at 50 ° C. for 30 minutes to almost completely remove water. The mixture thus obtained was compressed and tableted with the above tableting machine at a filling amount of 4.459 g per tablet to prepare 2500 fixing replenishing tablets D.

A developing solution having a pH of 10.70 and having the following composition, prepared by diluting the prepared developing replenishment tablet with dilution water: 16.5.
Add 330 ml of starter to 1 l
Was used as a development starting solution.

<Developer composition> Potassium carbonate 120.0 g / l Sodium erythorbate 40.0 g / l DTPA 5.0 g / l 1-Phenyl-5-mercaptotetrazole 0.05 g / l Sodium hydrogencarbonate 20.0 g / l Phenidone 3.0 g / l Sodium sulfite 15.0 g / l Polyhydric alcohol or polyethylene glycol described in Table 1 15.0 g / l Glutaraldehyde sulfite adduct 4.0 g / l <Developer starter> 210 g glacial acetic acid, KBr 530 g
To 1 liter by adding water.

A fixing replenishing tablet was prepared by diluting with fixing water to obtain a fixing starter solution having the following composition.

<Fixing starter composition> Ammonium thiosulfate 160.0 g / l Sodium sulfite 12.0 g / l Boric acid 1.0 g / l Sodium hydroxide 5.0 g / l Glacial acetic acid 10.0 g / l Aluminum sulfate-18-hydrate 35.0 g / l Sulfuric acid (50% by weight) 5.0 g / l Ethylenediaminetetraacetic acid disodium dihydrate 0.02 g / l (Processing) Solid processing agent charging member for automatic developing machine SRX-502 manufactured by Konica Corporation Equipped with a dry to dry 2
It was modified so that it could be processed in 0 seconds and was run.

[0120] For replenishment, 1 part of the above-mentioned agent A, ² parts of the agent B and 20 ml of water were added to the developing solution per 1.00 m ² of the light-sensitive material, and 4 parts of the above-mentioned agent C per 1.00 m ² of the light-sensitive material to the fixing solution. And D agent 2
This was carried out by adding 50 ml of water and 50 ml of water. The addition of water was started in synchronization with the addition of each treating agent, and was performed at a constant speed for 10 minutes substantially in proportion to the dissolution rate of the treating agent.

(Evaluation of Fog) In the evaluation of fog, each unexposed sample was treated in the same manner as in (1), and the density was measured with a microdensitometer.

(Evaluation of Silver Tone) Each sample was subjected to the same treatment as in (1) for silver tone determination, and the density was 1.2 ± 0.
X-ray exposure was performed so as to obtain 5, and the same treatment as in (1) was performed and evaluated.

The color tone judgment is based on the following criteria.

A: Pure black tone B: Slight yellowness is felt C: Yellowness is felt The results obtained above are shown in Table 1.

[0125]

[Table 1]

The sample of the present invention has high sensitivity, low fog, and excellent silver tone.

Example 2 EM-2 was prepared in the same manner as in Example 1.

(Chemical Sensitization of Emulsion) EM-2 was chemically sensitized in the same manner as in Example 1 except that the compound of the general formula (1) and the selenium sensitizer were not added.

(Preparation and coating of coating liquid) Dextran or dextrin or the following comparative latex was added to the emulsion layer in an amount of 0.3.
It was added so as to be g / m ^2, the amount of gelatin 0.5 g / m ²
The coating liquid was prepared and coated in the same manner as in Example 1 except that the above was adopted. In the comparative sample to which the above polymer was not added, 0.3 g / m ^{2 of} gelatin was further added.
Table 2 shows each additive compound of the obtained coating samples 101 to 108.

Preparation of the treatment agent, treatment, and evaluation of silver tone were carried out in the same manner as in Example 1, and the results are shown in Table 2.

[0131]

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(Evaluation of Remaining Color) For the evaluation of the residual color property, each unexposed sample was treated in the same manner as in (Evaluation of sensitivity), and 510 nm was applied.
Table 2
It was shown to. The residual color in the table indicates the developed sample No. It was expressed as a relative value when the value of 101 was 100. The lower the number,
It shows that the residual color is excellent.

In the same manner as (Evaluation of Roller Mark) (Evaluation of Silver Tone), each sample was exposed to X-rays and processed in the same manner. However, the developing rack used at this time and the developing-to-fixing transition rack were intentionally fatigued. That is, due to the fatigue of the rollers of each rack, irregularities of about 10 μm were formed on the entire surface. Due to the pressure caused by this unevenness in the processed sample, many fine spot-like density unevenness occurred in the sample with poor pressure resistance. This level was evaluated according to the following criteria.

A: No spot formation B: Small spot formation C: Large spot formation The above results are shown in Table 2.

[0135]

[Table 2]

It can be seen from Table 2 that the samples according to the present invention exhibit excellent effects in residual color, roller mark and silver tone.

[0137]

EFFECTS OF THE INVENTION According to the present invention, there is little influence on the human body at the time of handling, excellent silver color tone even with rapid processing, little residual color, high sensitivity and low fog, and excellent silver color tone. A method of processing a silver halide photographic light-sensitive material having less color and improved roller marks is obtained.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Internal reference number FI Technical indication G03C 5/305 G03C 5/305

Claims (2)

[Claims] 1. A selenium compound and / or a tellurium compound,
And processing a silver halide photographic light-sensitive material having at least one silver halide emulsion layer containing a compound represented by the following general formula (1) with a developer containing a polyhydric alcohol and reductones. A method for processing a silver halide photographic light-sensitive material, which is characterized. Formula _{(1) R 11 - (S} ) in n-R ₁₂ formula, R ₁₁ and R ₁₂ represents an aliphatic group, an aromatic group, a heterocyclic group, or combined with each other an atomic group which can form a ring Represent R ₁₁ and R ₁₂ may be the same or different. n
Represents an integer of 2 to 6. 2. A silver halide photographic light-sensitive material having at least one hydrophilic colloid layer containing dextrin and / or dextran is treated with a developer containing a polyhydric alcohol and reductones. A method for processing a silver halide photographic light-sensitive material.